WO2015020170A1 - Flat tire sealant - Google Patents
Flat tire sealant Download PDFInfo
- Publication number
- WO2015020170A1 WO2015020170A1 PCT/JP2014/070937 JP2014070937W WO2015020170A1 WO 2015020170 A1 WO2015020170 A1 WO 2015020170A1 JP 2014070937 W JP2014070937 W JP 2014070937W WO 2015020170 A1 WO2015020170 A1 WO 2015020170A1
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- WO
- WIPO (PCT)
- Prior art keywords
- copolymer resin
- vinyl versatate
- tire puncture
- vinyl
- versatate copolymer
- Prior art date
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
- B29C73/16—Auto-repairing or self-sealing arrangements or agents
- B29C73/163—Sealing compositions or agents, e.g. combined with propellant agents
Definitions
- the present invention relates to a tire puncture sealant.
- Patent Document 1 discloses a “tire puncture sealant containing a natural rubber latex, a synthetic resin emulsion, and propylene glycol”, wherein the synthetic resin contained in the synthetic resin emulsion is “ethylene-vinyl acetate-vinyl versatate copolymer”.
- a tire puncture sealant which is a “resin” is described ([Claim 1] and [Claim 3]).
- the present inventor made an unsaturated organic acid copolymerized with a vinyl versatate copolymer resin contained in a tire puncture sealant, without deteriorating storage performance.
- the present inventors have found that the low temperature injection performance can be improved and completed the present invention.
- the present invention provides the following (1) to (5).
- Natural rubber latex (A) and vinyl versatate copolymer resin emulsion (B) which is an emulsion of vinyl versatate copolymer resin (b1) containing vinyl versatate and unsaturated organic acid as monomer units, Contains tire puncture sealant.
- the vinyl versatate copolymer resin emulsion (B) contains an emulsifier (b2) containing polyvinyl alcohol, and the content of the emulsifier (b2) is that of the vinyl versatate copolymer resin emulsion (B).
- the tire puncture sealant according to (1) or (2) above which is 0.8 to 3.0% by mass with respect to the solid content.
- the mass ratio (A / B) of the solid content of the natural rubber latex (A) to the solid content of the vinyl versatate copolymer resin emulsion (B) is 90/10 to 40/60,
- the tire puncture sealant according to any one of (1) to (4).
- the tire puncture sealant of the present invention is a vinyl versatate copolymer emulsion which is an emulsion of natural rubber latex (A), vinyl versatate copolymer resin (b1) containing vinyl versatate and unsaturated organic acid as monomer units.
- reducing the emulsifier for dispersing the particles of the vinyl versatate copolymer resin (b1) can improve the low-temperature injection performance, but in this case, by reducing the emulsifier, The ionic repulsion between the particles becomes smaller and the particles approach each other, resulting in a decrease in storage performance.
- an unsaturated organic acid such as (meth) acrylic acid as a monomer unit constituting the vinyl versatate copolymer resin (b1)
- an acid group derived from the unsaturated organic acid appears on the particle surface.
- the natural rubber latex (A) is not particularly limited, and a conventionally known one can be used.
- a deproteinized natural rubber latex obtained by removing proteins from the natural rubber latex is preferable. This is because if the amount of protein is small, the amount of ammonia generated can be reduced, and corrosion damage to the steel cord due to ammonia and generation of an irritating odor can be prevented.
- deproteinized natural rubber latex (SeLatex series, manufactured by SRI Hybrid), deproteinized natural rubber latex (HA, manufactured by Nomura Trading Co., Ltd.), ultra-low ammonia natural rubber latex (ULACOL, manufactured by Restex), etc. Is mentioned.
- the natural rubber latex (A) may be used alone or in combination of two or more.
- the weight average molecular weight (Mw) of the natural rubber contained in the natural rubber latex (A) is not particularly limited.
- the weight average molecular weight is a weight average molecular weight expressed in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent (hereinafter the same).
- the tire puncture sealant of the present invention can further contain a synthetic rubber latex, such as SBR latex, NBR latex, carboxy-modified NBR latex, carboxy-modified SBR latex, and the like. Is mentioned.
- the vinyl versatate copolymer resin emulsion (B) is an emulsion in which the vinyl versatate copolymer resin (b1) is dispersed in a dispersion medium such as water as a dispersoid.
- a dispersion medium such as water as a dispersoid.
- the phase of the vinyl versatate copolymer resin (b1) which is a dispersoid may be a liquid phase or a solid phase.
- emulsion a system in which a dispersoid that is a liquid phase is dispersed in a dispersion medium that is a liquid phase
- emulsion a system in which a dispersoid that is a solid phase is dispersed in a dispersion medium that is a liquid phase
- emulsion is a concept including “suspension”.
- the vinyl versatate copolymer resin (b1) is a copolymer resin containing vinyl versatate (ester of versatic acid and vinyl alcohol) and an unsaturated organic acid as monomer units, that is, vinyl vinyl versatate and unsaturated organic acid. It is a copolymer resin composed of monomer units.
- the unsaturated organic acid is not particularly limited as long as it has an unsaturated bond and a carboxy group.
- unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; maleic acid, crotonic acid, itacone Unsaturated dicarboxylic acids such as acid, fumaric acid, muconic acid and citraconic acid; these unsaturated dicarboxylic acids and alkyl groups having about 1 to 18 carbon atoms (which may be linear, branched or cyclic) ), And the like. These may be used alone or in combination of two or more.
- unsaturated monocarboxylic acids and unsaturated dicarboxylic acids are preferable, and acrylic acid, methacrylic acid, itaconic acid and maleic acid are more preferable because the storage performance of the tire puncture sealant of the present invention is more excellent.
- acrylic acid and / or methacrylic acid is referred to as “(meth) acrylic acid”.
- examples of monomer units other than vinyl versatate and unsaturated organic acid include ethylene, vinyl acetate, and the like.
- the vinyl versatate copolymer resin (b1) can be, for example, a random copolymer, a block copolymer, or a graft polymer.
- vinyl versatate copolymer resin (b1) examples include, for example, unsaturated organic acid-ethylene-vinyl acetate-vinyl versatate copolymer resin, unsaturated organic acid-vinyl acetate-versaic acid.
- a vinyl copolymer resin etc. are mentioned, These may be used individually by 1 type and may use 2 or more types together.
- an unsaturated organic acid-ethylene-vinyl acetate-vinyl versatate copolymer resin is preferable because it contains ethylene and has a low viscosity.
- the weight average molecular weight (Mw) of the vinyl versatate copolymer resin (b1) is not particularly limited, but is preferably 10,000 to 500,000, more preferably 50,000 to 200,000.
- the glass transition point (Tg) of the vinyl versatate copolymer resin (b1) is not particularly limited, but is preferably about ⁇ 20 ° C. or lower, more preferably about ⁇ 25 ° C. or lower, and further about ⁇ 30 ° C. or lower. preferable.
- the glass transition point (Tg) is a thermogram measured by differential scanning calorimetry (DSC) under a temperature rising rate condition of 10 ° C./min, and is defined as the temperature at the midpoint of the transition region (the same applies hereinafter).
- the ratio of unsaturated organic acid to all monomer units constituting the vinyl versatate copolymer resin (b1) (hereinafter also referred to as “unsaturated organic acid amount” for convenience) is the tire of the present invention.
- the reason is that 0.01 to 2.00% by mass is preferable, and 0.15 to 0.50% by mass is more preferable because the storage performance and low temperature injection performance of the puncture sealant are more excellent.
- the ratio of monomers constituting the resin is preferably 0.01 to 2.00: 2.5 to 56: 2.5 to 56:20 to 90 in terms of mass ratio (hereinafter also referred to as “monomer mass ratio”). 15 to 0.50: 3 to 56: 3 to 56:20 to 90 is more preferable.
- the vinyl versatate copolymer resin emulsion (B) preferably contains an emulsifier (b2) containing polyvinyl alcohol. That is, it is preferable that the said vinyl versatate copolymer resin (b1) which is a dispersoid is disperse
- the said emulsifier (b2) may contain only polyvinyl alcohol and may contain emulsifier components other than polyvinyl alcohol.
- emulsifier components other than polyvinyl alcohol include protective colloids such as hydroxyethyl cellulose, methyl cellulose, and carboxymethyl cellulose; polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene / polyoxypropylene block copolymer, polyoxyethylene fatty acid ester
- Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters; alkyl sulfate esters, alkyl benzene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl phosphates
- Anionic surfactants such as esters; and the like, and these may be used alone, It may be used in combination with more species.
- Polyvinyl alcohol is also called poval, and is generally obtained by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate.
- polyvinyl alcohol low saponified PVA or completely saponified PVA may be used.
- partially saponified PVA having a saponification degree of 80 to 90 mol% is preferably used. The degree is preferably from 300 to 1,700.
- Polyvinyl alcohol may be modified with a compound such as carboxylic acid, sulfonic acid, or siloxane. Polyvinyl alcohol may be used alone or in combination of two or more.
- Emsifier amount In the vinyl versatate copolymer resin emulsion (B), the content of the emulsifier (b2) relative to the solid content of the vinyl vinyl versatate resin emulsion (B) (hereinafter also referred to as “emulsifier amount”) is 0. 8 to 3.0% by mass is preferable, and 1.2 to 2.0% by mass is more preferable.
- the amount of the emulsifier is within the above range, the storage performance and low-temperature injection performance of the tire puncture sealant of the present invention are more excellent.
- the tire puncture sealant may be thickened, but if the amount of the emulsifier is within the above range, thickening is suppressed and the low-temperature injection performance can be improved.
- the method for producing the vinyl versatate copolymer resin emulsion (B), which is an emulsion of the vinyl versatate copolymer resin (b1), is not particularly limited.
- a monomer containing vinyl versatate and an unsaturated organic acid And a method of producing (polymerizing) by a conventionally known emulsion polymerization method using the above-mentioned emulsifier (b2).
- the polymerization conditions are not particularly limited, but generally the polymerization temperature is 20 to 80 ° C.
- the catalyst include persulfates such as potassium persulfate, hydrogen peroxide, and various organic peroxides.
- the mass ratio (A / B) of the solid content of the natural rubber latex (A) and the solid content of the vinyl versatate copolymer resin emulsion (B) is 90/10 to 40. / 60 is preferable, and 50/50 to 70/30 is more preferable.
- the mass ratio (A / B) is in the above range, the storage performance and sealing performance of the tire puncture sealant of the present invention can be achieved at a high level.
- the solid contents of the natural rubber latex (A) and the vinyl versatate copolymer emulsion (B) are each a heating residue, specifically, heated at 200 ° C. for 1 hour. It is the amount of residue obtained later.
- the emulsifier (b2) is contained in the solid content of the vinyl versatate copolymer resin emulsion (B).
- the tire puncture sealant of the present invention preferably further contains propylene glycol (C) as an antifreeze agent.
- the mass ratio (B / C) between the solid content of the vinyl versatate copolymer emulsion (B) and the propylene glycol (C) is preferably 0.1 to 1.1, and preferably 0.3 to 0. .5 is more preferred.
- the mass ratio (B / C) is in the above range, the storage performance and sealing performance of the tire puncture sealant of the present invention can be achieved at a high level.
- the tire puncture sealant of the present invention may contain water as a solvent, but the mass ratio (C / water) between the propylene glycol (C) and water is preferably 0.9 to 1.8.
- the tire puncture sealant of the present invention may further contain an additive as required, in addition to the components described above.
- the additive include an antifreezing agent other than the propylene glycol (C) (for example, ethylene glycol, diethylene glycol, glycerin, etc.), a tackifier, a filler, an anti-aging agent, an antioxidant, and a pigment (dye). , Plasticizers, thixotropic agents, ultraviolet absorbers, flame retardants, surfactants (including leveling agents), dispersants, dehydrating agents, antistatic agents and the like.
- the amount of the additive is not particularly limited.
- the method for producing the tire puncture sealant of the present invention is not particularly limited.
- the tire puncture seal is obtained by sufficiently mixing the above-described essential components and optional components using a stirring machine such as a mixing mixer under reduced pressure.
- the method of manufacturing an agent is mentioned.
- the tire puncture sealant of the present invention is injected into the tire from the air filling portion of the tire.
- the method for injecting the tire puncture sealant of the present invention into the tire is not particularly limited, and a conventionally known method can be used, and examples thereof include a method using a syringe, a spray can and the like.
- the amount of the tire puncture sealant injected into the tire is not particularly limited, and is appropriately selected according to the size of the puncture hole.
- the tire is filled with air to a predetermined air pressure. Then, drive the car.
- Polymerization was started by adding to a pressure vessel. Subsequently, after confirming that the liquid temperature in the pressure resistant vessel had risen, while maintaining the liquid temperature in the vessel at 50 ° C., when 4 hours had elapsed after the start of polymerization, the oxidizing agent was added with 10% sodium persulfate and Switch to 2% tert-butyl hydroperoxide aqueous solution, add to the pressure vessel, cool the pressure vessel when the residual vinyl acetate monomer is less than 1%, remove unreacted ethylene gas, and generate The thing was taken out. In this way, a vinyl versatate copolymer resin emulsion was obtained. The solid content was 53% by mass and the glass transition temperature was ⁇ 30 ° C.
- a tire puncture sealant was produced by mixing the components shown in Table 1 below in the amounts (parts by mass) shown in the same table.
- the vinyl versatate copolymer resin emulsion produced as described above was used as the component (B).
- the “monomer mass ratio” and “emulsifier amount” of the vinyl versatate copolymer resin emulsion used are shown in Table 1 below. Monomers that were not used were marked with “-”.
- the lower numerical values (the numerical values in parentheses) in the components (A) and (B) are the total solid content of the components (A) and (B), respectively, in terms of the solid content.
- the evaluation criteria for sealing performance are “ ⁇ ” when the seal was completed within 5 cycles (no air leaks), “ ⁇ ” when the seal was sealed within 6 to 10 cycles, and when the seal was completed after 11 cycles. “ ⁇ ”, and “x” when the seal could not be made. If “ ⁇ ” or “ ⁇ ”, it can be evaluated as having excellent sealing performance.
- the viscosity of the obtained tire puncture sealant was measured at a rotational speed of 60 rpm using a BL type viscometer (rotor No. 4) under the condition of ⁇ 40 ° C.
- Comparative Examples 1 to 4 shown in Table 1 above it was found that reducing the amount of emulsifier on the basis of Comparative Example 1 improved the low-temperature injection performance while inferior storage performance.
- an unsaturated organic acid (acrylic acid or maleic acid) was copolymerized even when the amount of the emulsifier was reduced to the same level or lower as in Comparative Example 4 ( It was found that by using the component B), the low temperature injection performance can be improved while maintaining good storage performance. Further, from the results of Examples 7 and 8, it was found that the low-temperature injection performance can be improved by using the component (B) obtained by copolymerizing an unsaturated organic acid without reducing the amount of the emulsifier.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Sealing Material Composition (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Tires In General (AREA)
Abstract
The purpose of the present invention is to provide a flat tire sealant which exhibits excellent low-temperature injection performance and storage performance. This flat tire sealant contains natural rubber latex (A) and a versatic acid vinyl copolymer resin emulsion (B) which is an emulsion of a versatic acid vinyl copolymer resin (b1) containing versatic acid vinyl and an unsaturated organic acid as monomer units thereof.
Description
本発明は、タイヤパンクシール剤に関する。
The present invention relates to a tire puncture sealant.
特許文献１には、「天然ゴムラテックスと合成樹脂エマルジョンとプロピレングリコールとを含むタイヤパンクシール剤」であって、合成樹脂エマルジョンに含有される合成樹脂が「エチレン－酢酸ビニル－バーサチック酸ビニル共重合樹脂」であるタイヤパンクシール剤が記載されている（［請求項１］および［請求項３］）。
Patent Document 1 discloses a “tire puncture sealant containing a natural rubber latex, a synthetic resin emulsion, and propylene glycol”, wherein the synthetic resin contained in the synthetic resin emulsion is “ethylene-vinyl acetate-vinyl versatate copolymer”. A tire puncture sealant which is a “resin” is described ([Claim 1] and [Claim 3]).
近年、タイヤパンクシール剤に要求される性能のレベルが上がっており、とりわけ、低温環境下での注入性能（低温注入性能）などの低温特性の向上が求められている。
本発明者は、特許文献１に記載のタイヤパンクシール剤について検討を行なったところ、「エチレン－酢酸ビニル－バーサチック酸ビニル共重合樹脂」のエマルジョンに用いられる乳化剤量を低減することで、低温注入性能が改善されることを見出した。
しかしながら、このとき、乳化剤量を低減により、低温注入性能が改善される一方で、タイヤパンクシール剤の基本的な性能である保管性能が低下することが明らかとなった。
本発明は、以上の点を鑑みてなされたものであり、低温注入性能および保管性能がともに優れるタイヤパンクシール剤を提供することを目的とする。 In recent years, the level of performance required for tire puncture sealants has increased, and in particular, improvement in low temperature characteristics such as injection performance (low temperature injection performance) in a low temperature environment has been demanded.
The present inventor examined the tire puncture sealant described in Patent Document 1, and found that by reducing the amount of emulsifier used in the emulsion of “ethylene-vinyl acetate-vinyl versatate copolymer resin”, low-temperature injection was performed. We have found that the performance is improved.
However, at this time, it has been clarified that the storage performance, which is the basic performance of the tire puncture sealant, is lowered while the low temperature injection performance is improved by reducing the amount of the emulsifier.
This invention is made | formed in view of the above point, and it aims at providing the tire puncture sealant which is excellent in both low temperature injection | pouring performance and storage performance.
本発明者は、特許文献１に記載のタイヤパンクシール剤について検討を行なったところ、「エチレン－酢酸ビニル－バーサチック酸ビニル共重合樹脂」のエマルジョンに用いられる乳化剤量を低減することで、低温注入性能が改善されることを見出した。
しかしながら、このとき、乳化剤量を低減により、低温注入性能が改善される一方で、タイヤパンクシール剤の基本的な性能である保管性能が低下することが明らかとなった。
本発明は、以上の点を鑑みてなされたものであり、低温注入性能および保管性能がともに優れるタイヤパンクシール剤を提供することを目的とする。 In recent years, the level of performance required for tire puncture sealants has increased, and in particular, improvement in low temperature characteristics such as injection performance (low temperature injection performance) in a low temperature environment has been demanded.
The present inventor examined the tire puncture sealant described in Patent Document 1, and found that by reducing the amount of emulsifier used in the emulsion of “ethylene-vinyl acetate-vinyl versatate copolymer resin”, low-temperature injection was performed. We have found that the performance is improved.
However, at this time, it has been clarified that the storage performance, which is the basic performance of the tire puncture sealant, is lowered while the low temperature injection performance is improved by reducing the amount of the emulsifier.
This invention is made | formed in view of the above point, and it aims at providing the tire puncture sealant which is excellent in both low temperature injection | pouring performance and storage performance.
本発明者は、上記目的を達成するために鋭意検討した結果、タイヤパンクシール剤に含まれるバーサチック酸ビニル共重合樹脂に不飽和有機酸を共重合させることで、保管性能を低下させずに、低温注入性能を向上できることを見出し、本発明を完成させた。
As a result of intensive studies to achieve the above object, the present inventor made an unsaturated organic acid copolymerized with a vinyl versatate copolymer resin contained in a tire puncture sealant, without deteriorating storage performance. The present inventors have found that the low temperature injection performance can be improved and completed the present invention.
すなわち、本発明は、以下の（１）～（５）を提供する。
（１）天然ゴムラテックス（Ａ）と、バーサチック酸ビニルおよび不飽和有機酸をモノマー単位として含むバーサチック酸ビニル共重合樹脂（ｂ１）のエマルジョンであるバーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）と、を含有するタイヤパンクシール剤。
（２）上記バーサチック酸ビニル共重合樹脂（ｂ１）を構成する全モノマー単位に対する上記不飽和有機酸の割合が、０．０１～２．００質量％である、上記（１）に記載のタイヤパンクシール剤。
（３）上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）が、ポリビニルアルコールを含む乳化剤（ｂ２）を含有し、上記乳化剤（ｂ２）の含有量が、上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）の固形分に対して、０．８～３．０質量％である、上記（１）または（２）に記載のタイヤパンクシール剤。
（４）上記バーサチック酸ビニル共重合樹脂（ｂ１）が、不飽和有機酸－エチレン－酢酸ビニル－バーサチック酸ビニル共重合樹脂である、上記（１）～（３）のいずれかに記載のタイヤパンクシール剤。
（５）上記天然ゴムラテックス（Ａ）の固形分と上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）の固形分との質量比（Ａ／Ｂ）が、９０／１０～４０／６０である、上記（１）～（４）のいずれかに記載のタイヤパンクシール剤。 That is, the present invention provides the following (1) to (5).
(1) Natural rubber latex (A) and vinyl versatate copolymer resin emulsion (B) which is an emulsion of vinyl versatate copolymer resin (b1) containing vinyl versatate and unsaturated organic acid as monomer units, Contains tire puncture sealant.
(2) The tire puncture according to (1), wherein the ratio of the unsaturated organic acid to the total monomer units constituting the vinyl versatate copolymer resin (b1) is 0.01 to 2.00% by mass. Sealing agent.
(3) The vinyl versatate copolymer resin emulsion (B) contains an emulsifier (b2) containing polyvinyl alcohol, and the content of the emulsifier (b2) is that of the vinyl versatate copolymer resin emulsion (B). The tire puncture sealant according to (1) or (2) above, which is 0.8 to 3.0% by mass with respect to the solid content.
(4) The tire puncture according to any one of (1) to (3) above, wherein the vinyl versatate copolymer resin (b1) is an unsaturated organic acid-ethylene-vinyl acetate-vinyl versatate copolymer resin Sealing agent.
(5) The mass ratio (A / B) of the solid content of the natural rubber latex (A) to the solid content of the vinyl versatate copolymer resin emulsion (B) is 90/10 to 40/60, The tire puncture sealant according to any one of (1) to (4).
（１）天然ゴムラテックス（Ａ）と、バーサチック酸ビニルおよび不飽和有機酸をモノマー単位として含むバーサチック酸ビニル共重合樹脂（ｂ１）のエマルジョンであるバーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）と、を含有するタイヤパンクシール剤。
（２）上記バーサチック酸ビニル共重合樹脂（ｂ１）を構成する全モノマー単位に対する上記不飽和有機酸の割合が、０．０１～２．００質量％である、上記（１）に記載のタイヤパンクシール剤。
（３）上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）が、ポリビニルアルコールを含む乳化剤（ｂ２）を含有し、上記乳化剤（ｂ２）の含有量が、上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）の固形分に対して、０．８～３．０質量％である、上記（１）または（２）に記載のタイヤパンクシール剤。
（４）上記バーサチック酸ビニル共重合樹脂（ｂ１）が、不飽和有機酸－エチレン－酢酸ビニル－バーサチック酸ビニル共重合樹脂である、上記（１）～（３）のいずれかに記載のタイヤパンクシール剤。
（５）上記天然ゴムラテックス（Ａ）の固形分と上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）の固形分との質量比（Ａ／Ｂ）が、９０／１０～４０／６０である、上記（１）～（４）のいずれかに記載のタイヤパンクシール剤。 That is, the present invention provides the following (1) to (5).
(1) Natural rubber latex (A) and vinyl versatate copolymer resin emulsion (B) which is an emulsion of vinyl versatate copolymer resin (b1) containing vinyl versatate and unsaturated organic acid as monomer units, Contains tire puncture sealant.
(2) The tire puncture according to (1), wherein the ratio of the unsaturated organic acid to the total monomer units constituting the vinyl versatate copolymer resin (b1) is 0.01 to 2.00% by mass. Sealing agent.
(3) The vinyl versatate copolymer resin emulsion (B) contains an emulsifier (b2) containing polyvinyl alcohol, and the content of the emulsifier (b2) is that of the vinyl versatate copolymer resin emulsion (B). The tire puncture sealant according to (1) or (2) above, which is 0.8 to 3.0% by mass with respect to the solid content.
(4) The tire puncture according to any one of (1) to (3) above, wherein the vinyl versatate copolymer resin (b1) is an unsaturated organic acid-ethylene-vinyl acetate-vinyl versatate copolymer resin Sealing agent.
(5) The mass ratio (A / B) of the solid content of the natural rubber latex (A) to the solid content of the vinyl versatate copolymer resin emulsion (B) is 90/10 to 40/60, The tire puncture sealant according to any one of (1) to (4).
本発明によれば、低温注入性能および保管性能がともに優れるタイヤパンクシール剤を提供できる。
According to the present invention, it is possible to provide a tire puncture sealant that is excellent in both low temperature injection performance and storage performance.
［タイヤパンクシール剤］
本発明のタイヤパンクシール剤は、天然ゴムラテックス（Ａ）と、バーサチック酸ビニルおよび不飽和有機酸をモノマー単位として含むバーサチック酸ビニル共重合樹脂（ｂ１）のエマルジョンであるバーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）と、を含有するタイヤパンクシール剤である。 [Tire puncture sealant]
The tire puncture sealant of the present invention is a vinyl versatate copolymer emulsion which is an emulsion of natural rubber latex (A), vinyl versatate copolymer resin (b1) containing vinyl versatate and unsaturated organic acid as monomer units. A tire puncture sealant containing (B).
本発明のタイヤパンクシール剤は、天然ゴムラテックス（Ａ）と、バーサチック酸ビニルおよび不飽和有機酸をモノマー単位として含むバーサチック酸ビニル共重合樹脂（ｂ１）のエマルジョンであるバーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）と、を含有するタイヤパンクシール剤である。 [Tire puncture sealant]
The tire puncture sealant of the present invention is a vinyl versatate copolymer emulsion which is an emulsion of natural rubber latex (A), vinyl versatate copolymer resin (b1) containing vinyl versatate and unsaturated organic acid as monomer units. A tire puncture sealant containing (B).
例えば、上記バーサチック酸ビニル共重合樹脂（ｂ１）の粒子を分散させる乳化剤（後述する乳化剤（ｂ２）を参照）を減らすと、低温注入性能を向上できるが、この場合、乳化剤が少なくなることで、粒子どうしのイオン斥力が小さくなって粒子どうしが接近し、保管性能が低下する。
しかしながら、上記バーサチック酸ビニル共重合樹脂（ｂ１）を構成するモノマー単位として（メタ）アクリル酸などの不飽和有機酸を共重合させることで、不飽和有機酸に由来する酸基が粒子表面に現れ、これにより、粒子どうしのイオン斥力が大きくなり、たとえ乳化剤を減らしても、保管性能を低下させずに、低温注入性能を向上できる。
なお、上記メカニズムは推測であり、これ以外のメカニズムであっても、本発明の範囲内とする。
以下、本発明のタイヤパンクシール剤が含有する各成分について詳述する。 For example, reducing the emulsifier for dispersing the particles of the vinyl versatate copolymer resin (b1) (see the emulsifier (b2) described later) can improve the low-temperature injection performance, but in this case, by reducing the emulsifier, The ionic repulsion between the particles becomes smaller and the particles approach each other, resulting in a decrease in storage performance.
However, by copolymerizing an unsaturated organic acid such as (meth) acrylic acid as a monomer unit constituting the vinyl versatate copolymer resin (b1), an acid group derived from the unsaturated organic acid appears on the particle surface. As a result, the ionic repulsion between the particles increases, and even if the emulsifier is reduced, the low temperature injection performance can be improved without deteriorating the storage performance.
The above mechanism is speculation, and other mechanisms are also within the scope of the present invention.
Hereinafter, each component contained in the tire puncture sealant of the present invention will be described in detail.
しかしながら、上記バーサチック酸ビニル共重合樹脂（ｂ１）を構成するモノマー単位として（メタ）アクリル酸などの不飽和有機酸を共重合させることで、不飽和有機酸に由来する酸基が粒子表面に現れ、これにより、粒子どうしのイオン斥力が大きくなり、たとえ乳化剤を減らしても、保管性能を低下させずに、低温注入性能を向上できる。
なお、上記メカニズムは推測であり、これ以外のメカニズムであっても、本発明の範囲内とする。
以下、本発明のタイヤパンクシール剤が含有する各成分について詳述する。 For example, reducing the emulsifier for dispersing the particles of the vinyl versatate copolymer resin (b1) (see the emulsifier (b2) described later) can improve the low-temperature injection performance, but in this case, by reducing the emulsifier, The ionic repulsion between the particles becomes smaller and the particles approach each other, resulting in a decrease in storage performance.
However, by copolymerizing an unsaturated organic acid such as (meth) acrylic acid as a monomer unit constituting the vinyl versatate copolymer resin (b1), an acid group derived from the unsaturated organic acid appears on the particle surface. As a result, the ionic repulsion between the particles increases, and even if the emulsifier is reduced, the low temperature injection performance can be improved without deteriorating the storage performance.
The above mechanism is speculation, and other mechanisms are also within the scope of the present invention.
Hereinafter, each component contained in the tire puncture sealant of the present invention will be described in detail.
〔天然ゴムラテックス（Ａ）〕
上記天然ゴムラテックス（Ａ）としては、特に限定されず、従来公知のものを使用でき、例えば、天然ゴムラテックスからタンパク質を除去した脱蛋白天然ゴムラテックスが好適に挙げられる。タンパク質が少ないと、アンモニアの発生量を少なくでき、アンモニアによるスチールコードへの腐食損傷および刺激臭の発生を防止するという理由からである。具体的には、例えば、脱蛋白天然ゴムラテックス（ＳｅＬａｔｅｘシリーズ、ＳＲＩハイブリッド社製）、脱蛋白天然ゴムラテックス（ＨＡ、野村貿易社製）、超低アンモニア天然ゴムラテックス（ＵＬＡＣＯＬ、レヂテックス社製）等が挙げられる。
上記天然ゴムラテックス（Ａ）は、１種単独で用いてもよく、２種以上を併用してもよい。 [Natural rubber latex (A)]
The natural rubber latex (A) is not particularly limited, and a conventionally known one can be used. For example, a deproteinized natural rubber latex obtained by removing proteins from the natural rubber latex is preferable. This is because if the amount of protein is small, the amount of ammonia generated can be reduced, and corrosion damage to the steel cord due to ammonia and generation of an irritating odor can be prevented. Specifically, for example, deproteinized natural rubber latex (SeLatex series, manufactured by SRI Hybrid), deproteinized natural rubber latex (HA, manufactured by Nomura Trading Co., Ltd.), ultra-low ammonia natural rubber latex (ULACOL, manufactured by Restex), etc. Is mentioned.
The natural rubber latex (A) may be used alone or in combination of two or more.
上記天然ゴムラテックス（Ａ）としては、特に限定されず、従来公知のものを使用でき、例えば、天然ゴムラテックスからタンパク質を除去した脱蛋白天然ゴムラテックスが好適に挙げられる。タンパク質が少ないと、アンモニアの発生量を少なくでき、アンモニアによるスチールコードへの腐食損傷および刺激臭の発生を防止するという理由からである。具体的には、例えば、脱蛋白天然ゴムラテックス（ＳｅＬａｔｅｘシリーズ、ＳＲＩハイブリッド社製）、脱蛋白天然ゴムラテックス（ＨＡ、野村貿易社製）、超低アンモニア天然ゴムラテックス（ＵＬＡＣＯＬ、レヂテックス社製）等が挙げられる。
上記天然ゴムラテックス（Ａ）は、１種単独で用いてもよく、２種以上を併用してもよい。 [Natural rubber latex (A)]
The natural rubber latex (A) is not particularly limited, and a conventionally known one can be used. For example, a deproteinized natural rubber latex obtained by removing proteins from the natural rubber latex is preferable. This is because if the amount of protein is small, the amount of ammonia generated can be reduced, and corrosion damage to the steel cord due to ammonia and generation of an irritating odor can be prevented. Specifically, for example, deproteinized natural rubber latex (SeLatex series, manufactured by SRI Hybrid), deproteinized natural rubber latex (HA, manufactured by Nomura Trading Co., Ltd.), ultra-low ammonia natural rubber latex (ULACOL, manufactured by Restex), etc. Is mentioned.
The natural rubber latex (A) may be used alone or in combination of two or more.
上記天然ゴムラテックス（Ａ）に含まれる天然ゴムの重量平均分子量（Ｍｗ）は、特に限定されない。
なお、重量平均分子量は、テトラヒドロフランを溶媒とするゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）によりポリスチレン換算で表わされる重量平均分子量である（以下、同様）。 The weight average molecular weight (Mw) of the natural rubber contained in the natural rubber latex (A) is not particularly limited.
The weight average molecular weight is a weight average molecular weight expressed in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent (hereinafter the same).
なお、重量平均分子量は、テトラヒドロフランを溶媒とするゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）によりポリスチレン換算で表わされる重量平均分子量である（以下、同様）。 The weight average molecular weight (Mw) of the natural rubber contained in the natural rubber latex (A) is not particularly limited.
The weight average molecular weight is a weight average molecular weight expressed in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent (hereinafter the same).
また、本発明のタイヤパンクシール剤は、上記天然ゴムラテックス（Ａ）の他に、さらに合成ゴムラテックスを含むことができ、例えば、ＳＢＲラテックス、ＮＢＲラテックス、カルボキシ変性ＮＢＲラテックス、カルボキシ変性ＳＢＲラテックス等が挙げられる。
In addition to the natural rubber latex (A), the tire puncture sealant of the present invention can further contain a synthetic rubber latex, such as SBR latex, NBR latex, carboxy-modified NBR latex, carboxy-modified SBR latex, and the like. Is mentioned.
〔バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）〕
上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）は、バーサチック酸ビニル共重合樹脂（ｂ１）が分散質として、水等の分散媒に分散しているエマルジョンである。
このとき、分散質である上記バーサチック酸ビニル共重合樹脂（ｂ１）の相は、液相であっても固相であってもよい。
すなわち、一般的には、液相である分散媒に液相である分散質が分散した系を「エマルジョン」と呼び、液相である分散媒に固相である分散質が分散した系を「サスペンション」と呼ぶが、本発明では、「エマルジョン」は「サスペンション」を含む概念とする。 [Versatic acid vinyl copolymer resin emulsion (B)]
The vinyl versatate copolymer resin emulsion (B) is an emulsion in which the vinyl versatate copolymer resin (b1) is dispersed in a dispersion medium such as water as a dispersoid.
At this time, the phase of the vinyl versatate copolymer resin (b1) which is a dispersoid may be a liquid phase or a solid phase.
That is, in general, a system in which a dispersoid that is a liquid phase is dispersed in a dispersion medium that is a liquid phase is called an “emulsion”, and a system in which a dispersoid that is a solid phase is dispersed in a dispersion medium that is a liquid phase is referred to as “ In the present invention, “emulsion” is a concept including “suspension”.
上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）は、バーサチック酸ビニル共重合樹脂（ｂ１）が分散質として、水等の分散媒に分散しているエマルジョンである。
このとき、分散質である上記バーサチック酸ビニル共重合樹脂（ｂ１）の相は、液相であっても固相であってもよい。
すなわち、一般的には、液相である分散媒に液相である分散質が分散した系を「エマルジョン」と呼び、液相である分散媒に固相である分散質が分散した系を「サスペンション」と呼ぶが、本発明では、「エマルジョン」は「サスペンション」を含む概念とする。 [Versatic acid vinyl copolymer resin emulsion (B)]
The vinyl versatate copolymer resin emulsion (B) is an emulsion in which the vinyl versatate copolymer resin (b1) is dispersed in a dispersion medium such as water as a dispersoid.
At this time, the phase of the vinyl versatate copolymer resin (b1) which is a dispersoid may be a liquid phase or a solid phase.
That is, in general, a system in which a dispersoid that is a liquid phase is dispersed in a dispersion medium that is a liquid phase is called an “emulsion”, and a system in which a dispersoid that is a solid phase is dispersed in a dispersion medium that is a liquid phase is referred to as “ In the present invention, “emulsion” is a concept including “suspension”.
＜バーサチック酸ビニル共重合樹脂（ｂ１）＞
上記バーサチック酸ビニル共重合樹脂（ｂ１）は、バーサチック酸ビニル（バーサチック酸とビニルアルコールとのエステル）および不飽和有機酸をモノマー単位として含む共重合樹脂、すなわち、バーサチック酸ビニルおよび不飽和有機酸を含むモノマー単位で構成される共重合樹脂である。 <Versatic acid vinyl copolymer resin (b1)>
The vinyl versatate copolymer resin (b1) is a copolymer resin containing vinyl versatate (ester of versatic acid and vinyl alcohol) and an unsaturated organic acid as monomer units, that is, vinyl vinyl versatate and unsaturated organic acid. It is a copolymer resin composed of monomer units.
上記バーサチック酸ビニル共重合樹脂（ｂ１）は、バーサチック酸ビニル（バーサチック酸とビニルアルコールとのエステル）および不飽和有機酸をモノマー単位として含む共重合樹脂、すなわち、バーサチック酸ビニルおよび不飽和有機酸を含むモノマー単位で構成される共重合樹脂である。 <Versatic acid vinyl copolymer resin (b1)>
The vinyl versatate copolymer resin (b1) is a copolymer resin containing vinyl versatate (ester of versatic acid and vinyl alcohol) and an unsaturated organic acid as monomer units, that is, vinyl vinyl versatate and unsaturated organic acid. It is a copolymer resin composed of monomer units.
ここで、不飽和有機酸としては、不飽和結合およびカルボキシ基を有するものであれば、特に限定されず、例えば、アクリル酸、メタクリル酸などの不飽和モノカルボン酸類；マレイン酸、クロトン酸、イタコン酸、フマル酸、ムコン酸、シトラコン酸などの不飽和ジカルボン酸類；これらの不飽和ジカルボン酸類と炭素数１～１８程度のアルキル基（直鎖状、分岐鎖状、環状のいずれであってもよい）を有するアルコールとをエステル結合させてなる不飽和ジカルボン酸半エステル類；等が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。
これらのうち、不飽和モノカルボン酸類、不飽和ジカルボン酸類が好ましく、本発明のタイヤパンクシール剤の保管性能がより優れるという理由から、アクリル酸、メタクリル酸、イタコン酸、マレイン酸がより好ましい。
なお、本明細書では、アクリル酸および／またはメタクリル酸を、「（メタ）アクリル酸」と称する。 Here, the unsaturated organic acid is not particularly limited as long as it has an unsaturated bond and a carboxy group. For example, unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; maleic acid, crotonic acid, itacone Unsaturated dicarboxylic acids such as acid, fumaric acid, muconic acid and citraconic acid; these unsaturated dicarboxylic acids and alkyl groups having about 1 to 18 carbon atoms (which may be linear, branched or cyclic) ), And the like. These may be used alone or in combination of two or more.
Of these, unsaturated monocarboxylic acids and unsaturated dicarboxylic acids are preferable, and acrylic acid, methacrylic acid, itaconic acid and maleic acid are more preferable because the storage performance of the tire puncture sealant of the present invention is more excellent.
In the present specification, acrylic acid and / or methacrylic acid is referred to as “(meth) acrylic acid”.
これらのうち、不飽和モノカルボン酸類、不飽和ジカルボン酸類が好ましく、本発明のタイヤパンクシール剤の保管性能がより優れるという理由から、アクリル酸、メタクリル酸、イタコン酸、マレイン酸がより好ましい。
なお、本明細書では、アクリル酸および／またはメタクリル酸を、「（メタ）アクリル酸」と称する。 Here, the unsaturated organic acid is not particularly limited as long as it has an unsaturated bond and a carboxy group. For example, unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; maleic acid, crotonic acid, itacone Unsaturated dicarboxylic acids such as acid, fumaric acid, muconic acid and citraconic acid; these unsaturated dicarboxylic acids and alkyl groups having about 1 to 18 carbon atoms (which may be linear, branched or cyclic) ), And the like. These may be used alone or in combination of two or more.
Of these, unsaturated monocarboxylic acids and unsaturated dicarboxylic acids are preferable, and acrylic acid, methacrylic acid, itaconic acid and maleic acid are more preferable because the storage performance of the tire puncture sealant of the present invention is more excellent.
In the present specification, acrylic acid and / or methacrylic acid is referred to as “(meth) acrylic acid”.
また、バーサチック酸ビニル、不飽和有機酸以外のモノマー単位としては、例えば、エチレン、酢酸ビニル等が好適に挙げられる。
なお、上記バーサチック酸ビニル共重合樹脂（ｂ１）は、例えば、ランダム共重合体、ブロック共重合体、グラフト重合体とすることができる。 Further, examples of monomer units other than vinyl versatate and unsaturated organic acid include ethylene, vinyl acetate, and the like.
The vinyl versatate copolymer resin (b1) can be, for example, a random copolymer, a block copolymer, or a graft polymer.
なお、上記バーサチック酸ビニル共重合樹脂（ｂ１）は、例えば、ランダム共重合体、ブロック共重合体、グラフト重合体とすることができる。 Further, examples of monomer units other than vinyl versatate and unsaturated organic acid include ethylene, vinyl acetate, and the like.
The vinyl versatate copolymer resin (b1) can be, for example, a random copolymer, a block copolymer, or a graft polymer.
このような上記バーサチック酸ビニル共重合樹脂（ｂ１）としては、具体的には、例えば、不飽和有機酸－エチレン－酢酸ビニル－バーサチック酸ビニル共重合樹脂、不飽和有機酸－酢酸ビニル－バーサチック酸ビニル共重合樹脂などが挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。
これらのうち、エチレンを含むことで低粘度であるという理由から、不飽和有機酸－エチレン－酢酸ビニル－バーサチック酸ビニル共重合樹脂が好ましい。 Specific examples of the vinyl versatate copolymer resin (b1) include, for example, unsaturated organic acid-ethylene-vinyl acetate-vinyl versatate copolymer resin, unsaturated organic acid-vinyl acetate-versaic acid. A vinyl copolymer resin etc. are mentioned, These may be used individually by 1 type and may use 2 or more types together.
Among these, an unsaturated organic acid-ethylene-vinyl acetate-vinyl versatate copolymer resin is preferable because it contains ethylene and has a low viscosity.
これらのうち、エチレンを含むことで低粘度であるという理由から、不飽和有機酸－エチレン－酢酸ビニル－バーサチック酸ビニル共重合樹脂が好ましい。 Specific examples of the vinyl versatate copolymer resin (b1) include, for example, unsaturated organic acid-ethylene-vinyl acetate-vinyl versatate copolymer resin, unsaturated organic acid-vinyl acetate-versaic acid. A vinyl copolymer resin etc. are mentioned, These may be used individually by 1 type and may use 2 or more types together.
Among these, an unsaturated organic acid-ethylene-vinyl acetate-vinyl versatate copolymer resin is preferable because it contains ethylene and has a low viscosity.
なお、上記バーサチック酸ビニル共重合樹脂（ｂ１）の重量平均分子量（Ｍｗ）は、特に限定されないが、１０，０００～５００，０００が好ましく、５０，０００～２００，０００がより好ましい。
また、上記バーサチック酸ビニル共重合樹脂（ｂ１）のガラス転移点（Ｔｇ）は、特に限定されないが、約－２０℃以下が好ましく、約－２５℃以下がより好ましく、約－３０℃以下がさらに好ましい。
ここで、ガラス転移点（Ｔｇ）は、示差走査熱量測定（ＤＳＣ）により１０℃／分の昇温速度条件によりサーモグラムを測定し、転移域の中点の温度とする（以下、同様）。 The weight average molecular weight (Mw) of the vinyl versatate copolymer resin (b1) is not particularly limited, but is preferably 10,000 to 500,000, more preferably 50,000 to 200,000.
The glass transition point (Tg) of the vinyl versatate copolymer resin (b1) is not particularly limited, but is preferably about −20 ° C. or lower, more preferably about −25 ° C. or lower, and further about −30 ° C. or lower. preferable.
Here, the glass transition point (Tg) is a thermogram measured by differential scanning calorimetry (DSC) under a temperature rising rate condition of 10 ° C./min, and is defined as the temperature at the midpoint of the transition region (the same applies hereinafter).
また、上記バーサチック酸ビニル共重合樹脂（ｂ１）のガラス転移点（Ｔｇ）は、特に限定されないが、約－２０℃以下が好ましく、約－２５℃以下がより好ましく、約－３０℃以下がさらに好ましい。
ここで、ガラス転移点（Ｔｇ）は、示差走査熱量測定（ＤＳＣ）により１０℃／分の昇温速度条件によりサーモグラムを測定し、転移域の中点の温度とする（以下、同様）。 The weight average molecular weight (Mw) of the vinyl versatate copolymer resin (b1) is not particularly limited, but is preferably 10,000 to 500,000, more preferably 50,000 to 200,000.
The glass transition point (Tg) of the vinyl versatate copolymer resin (b1) is not particularly limited, but is preferably about −20 ° C. or lower, more preferably about −25 ° C. or lower, and further about −30 ° C. or lower. preferable.
Here, the glass transition point (Tg) is a thermogram measured by differential scanning calorimetry (DSC) under a temperature rising rate condition of 10 ° C./min, and is defined as the temperature at the midpoint of the transition region (the same applies hereinafter).
（不飽和有機酸量）
本発明においては、上記バーサチック酸ビニル共重合樹脂（ｂ１）を構成する全モノマー単位に対する不飽和有機酸の割合（以下、便宜的に「不飽和有機酸量」ともいう）は、本発明のタイヤパンクシール剤の保管性能および低温注入性能がより優れるという理由から、０．０１～２．００質量％が好ましく、０．１５～０．５０質量％がより好ましい。 (Unsaturated organic acid amount)
In the present invention, the ratio of unsaturated organic acid to all monomer units constituting the vinyl versatate copolymer resin (b1) (hereinafter also referred to as “unsaturated organic acid amount” for convenience) is the tire of the present invention. The reason is that 0.01 to 2.00% by mass is preferable, and 0.15 to 0.50% by mass is more preferable because the storage performance and low temperature injection performance of the puncture sealant are more excellent.
本発明においては、上記バーサチック酸ビニル共重合樹脂（ｂ１）を構成する全モノマー単位に対する不飽和有機酸の割合（以下、便宜的に「不飽和有機酸量」ともいう）は、本発明のタイヤパンクシール剤の保管性能および低温注入性能がより優れるという理由から、０．０１～２．００質量％が好ましく、０．１５～０．５０質量％がより好ましい。 (Unsaturated organic acid amount)
In the present invention, the ratio of unsaturated organic acid to all monomer units constituting the vinyl versatate copolymer resin (b1) (hereinafter also referred to as “unsaturated organic acid amount” for convenience) is the tire of the present invention. The reason is that 0.01 to 2.00% by mass is preferable, and 0.15 to 0.50% by mass is more preferable because the storage performance and low temperature injection performance of the puncture sealant are more excellent.
（モノマー質量比）
上記バーサチック酸ビニル共重合樹脂（ｂ１）が、不飽和有機酸－エチレン－酢酸ビニル－バーサチック酸ビニル共重合樹脂の場合、この樹脂を構成するモノマー比（不飽和有機酸：エチレン：酢酸ビニル：バーサチック酸ビニル）は、質量比（以下、これを「モノマー質量比」ともいう）で、０．０１～２．００：２．５～５６：２．５～５６：２０～９０が好ましく、０．１５～０．５０：３～５６：３～５６：２０～９０がより好ましい。 (Monomer mass ratio)
In the case where the vinyl versatate copolymer resin (b1) is an unsaturated organic acid-ethylene-vinyl acetate-vinyl versatate copolymer resin, the ratio of monomers constituting the resin (unsaturated organic acid: ethylene: vinyl acetate: versatic The vinyl acid) is preferably 0.01 to 2.00: 2.5 to 56: 2.5 to 56:20 to 90 in terms of mass ratio (hereinafter also referred to as “monomer mass ratio”). 15 to 0.50: 3 to 56: 3 to 56:20 to 90 is more preferable.
上記バーサチック酸ビニル共重合樹脂（ｂ１）が、不飽和有機酸－エチレン－酢酸ビニル－バーサチック酸ビニル共重合樹脂の場合、この樹脂を構成するモノマー比（不飽和有機酸：エチレン：酢酸ビニル：バーサチック酸ビニル）は、質量比（以下、これを「モノマー質量比」ともいう）で、０．０１～２．００：２．５～５６：２．５～５６：２０～９０が好ましく、０．１５～０．５０：３～５６：３～５６：２０～９０がより好ましい。 (Monomer mass ratio)
In the case where the vinyl versatate copolymer resin (b1) is an unsaturated organic acid-ethylene-vinyl acetate-vinyl versatate copolymer resin, the ratio of monomers constituting the resin (unsaturated organic acid: ethylene: vinyl acetate: versatic The vinyl acid) is preferably 0.01 to 2.00: 2.5 to 56: 2.5 to 56:20 to 90 in terms of mass ratio (hereinafter also referred to as “monomer mass ratio”). 15 to 0.50: 3 to 56: 3 to 56:20 to 90 is more preferable.
＜乳化剤（ｂ２）＞
上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）は、ポリビニルアルコールを含む乳化剤（ｂ２）を含有するのが好ましい。すなわち、分散質である上記バーサチック酸ビニル共重合樹脂（ｂ１）は、上記乳化剤（ｂ２）の作用によって、分散媒中に分散しているのが好ましい。
なお、上記乳化剤（ｂ２）は、ポリビニルアルコールのみを含有していてもよく、ポリビニルアルコール以外の乳化剤成分を含有していてもよい。ポリビニルアルコール以外の乳化剤成分としては、例えば、ヒドロキシエチルセルロース、メチルセルロース、カルボキシメチルセルロースなどの保護コロイド；ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェノールエーテル、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステルなどのノニオン系界面活性剤；アルキル硫酸エステル塩、アルキルベンゼンスルフォン酸塩、アルキルスルホコハク酸塩、アルキルジフェニルエーテルジスルフォン酸塩、ポリオキシエチレンアルキル硫酸塩、ポリオキシエチレンアルキルリン酸エステルなどのアニオン系界面活性剤；等が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。 <Emulsifier (b2)>
The vinyl versatate copolymer resin emulsion (B) preferably contains an emulsifier (b2) containing polyvinyl alcohol. That is, it is preferable that the said vinyl versatate copolymer resin (b1) which is a dispersoid is disperse | distributing in the dispersion medium by the effect | action of the said emulsifier (b2).
In addition, the said emulsifier (b2) may contain only polyvinyl alcohol and may contain emulsifier components other than polyvinyl alcohol. Examples of emulsifier components other than polyvinyl alcohol include protective colloids such as hydroxyethyl cellulose, methyl cellulose, and carboxymethyl cellulose; polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene / polyoxypropylene block copolymer, polyoxyethylene fatty acid ester Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters; alkyl sulfate esters, alkyl benzene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl phosphates Anionic surfactants such as esters; and the like, and these may be used alone, It may be used in combination with more species.
上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）は、ポリビニルアルコールを含む乳化剤（ｂ２）を含有するのが好ましい。すなわち、分散質である上記バーサチック酸ビニル共重合樹脂（ｂ１）は、上記乳化剤（ｂ２）の作用によって、分散媒中に分散しているのが好ましい。
なお、上記乳化剤（ｂ２）は、ポリビニルアルコールのみを含有していてもよく、ポリビニルアルコール以外の乳化剤成分を含有していてもよい。ポリビニルアルコール以外の乳化剤成分としては、例えば、ヒドロキシエチルセルロース、メチルセルロース、カルボキシメチルセルロースなどの保護コロイド；ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェノールエーテル、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステルなどのノニオン系界面活性剤；アルキル硫酸エステル塩、アルキルベンゼンスルフォン酸塩、アルキルスルホコハク酸塩、アルキルジフェニルエーテルジスルフォン酸塩、ポリオキシエチレンアルキル硫酸塩、ポリオキシエチレンアルキルリン酸エステルなどのアニオン系界面活性剤；等が挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。 <Emulsifier (b2)>
The vinyl versatate copolymer resin emulsion (B) preferably contains an emulsifier (b2) containing polyvinyl alcohol. That is, it is preferable that the said vinyl versatate copolymer resin (b1) which is a dispersoid is disperse | distributing in the dispersion medium by the effect | action of the said emulsifier (b2).
In addition, the said emulsifier (b2) may contain only polyvinyl alcohol and may contain emulsifier components other than polyvinyl alcohol. Examples of emulsifier components other than polyvinyl alcohol include protective colloids such as hydroxyethyl cellulose, methyl cellulose, and carboxymethyl cellulose; polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene / polyoxypropylene block copolymer, polyoxyethylene fatty acid ester Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters; alkyl sulfate esters, alkyl benzene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl phosphates Anionic surfactants such as esters; and the like, and these may be used alone, It may be used in combination with more species.
ポリビニルアルコール（ＰＶＡ）は、ポバールとも呼ばれ、一般的に、酢酸ビニルを重合したポリ酢酸ビニルをケン化して得られるものである。このようなポリビニルアルコールとしては、低ケン化ＰＶＡや完全ケン化ＰＶＡを使用してもよいが、例えば、ケン化度が８０～９０モル％の部分ケン化ＰＶＡが好適に用いられ、また、重合度は３００～１，７００が好ましい。
また、ポリビニルアルコールは、カルボン酸、スルホン酸、シロキサン等の化合物で変性されたものであってもよい。
ポリビニルアルコールは、１種単独で用いてもよく、２種以上を併用してもよい。 Polyvinyl alcohol (PVA) is also called poval, and is generally obtained by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate. As such polyvinyl alcohol, low saponified PVA or completely saponified PVA may be used. For example, partially saponified PVA having a saponification degree of 80 to 90 mol% is preferably used. The degree is preferably from 300 to 1,700.
Polyvinyl alcohol may be modified with a compound such as carboxylic acid, sulfonic acid, or siloxane.
Polyvinyl alcohol may be used alone or in combination of two or more.
また、ポリビニルアルコールは、カルボン酸、スルホン酸、シロキサン等の化合物で変性されたものであってもよい。
ポリビニルアルコールは、１種単独で用いてもよく、２種以上を併用してもよい。 Polyvinyl alcohol (PVA) is also called poval, and is generally obtained by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate. As such polyvinyl alcohol, low saponified PVA or completely saponified PVA may be used. For example, partially saponified PVA having a saponification degree of 80 to 90 mol% is preferably used. The degree is preferably from 300 to 1,700.
Polyvinyl alcohol may be modified with a compound such as carboxylic acid, sulfonic acid, or siloxane.
Polyvinyl alcohol may be used alone or in combination of two or more.
（乳化剤量）
上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）において、上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）の固形分に対する上記乳化剤（ｂ２）の含有量（以下、「乳化剤量」ともいう）は、０．８～３．０質量％が好ましく、１．２～２．０質量％がより好ましい。
上記乳化剤量が上記範囲であれば、本発明のタイヤパンクシール剤の保管性能および低温注入性能がより優れる。
とりわけ、ポリビニルアルコールが多すぎるとタイヤパンクシール剤が増粘する可能性があるが、上記乳化剤量が上記範囲であれば、増粘が抑制され、低温注入性能をより良好にできる。 (Emulsifier amount)
In the vinyl versatate copolymer resin emulsion (B), the content of the emulsifier (b2) relative to the solid content of the vinyl vinyl versatate resin emulsion (B) (hereinafter also referred to as “emulsifier amount”) is 0. 8 to 3.0% by mass is preferable, and 1.2 to 2.0% by mass is more preferable.
When the amount of the emulsifier is within the above range, the storage performance and low-temperature injection performance of the tire puncture sealant of the present invention are more excellent.
In particular, if there is too much polyvinyl alcohol, the tire puncture sealant may be thickened, but if the amount of the emulsifier is within the above range, thickening is suppressed and the low-temperature injection performance can be improved.
上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）において、上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）の固形分に対する上記乳化剤（ｂ２）の含有量（以下、「乳化剤量」ともいう）は、０．８～３．０質量％が好ましく、１．２～２．０質量％がより好ましい。
上記乳化剤量が上記範囲であれば、本発明のタイヤパンクシール剤の保管性能および低温注入性能がより優れる。
とりわけ、ポリビニルアルコールが多すぎるとタイヤパンクシール剤が増粘する可能性があるが、上記乳化剤量が上記範囲であれば、増粘が抑制され、低温注入性能をより良好にできる。 (Emulsifier amount)
In the vinyl versatate copolymer resin emulsion (B), the content of the emulsifier (b2) relative to the solid content of the vinyl vinyl versatate resin emulsion (B) (hereinafter also referred to as “emulsifier amount”) is 0. 8 to 3.0% by mass is preferable, and 1.2 to 2.0% by mass is more preferable.
When the amount of the emulsifier is within the above range, the storage performance and low-temperature injection performance of the tire puncture sealant of the present invention are more excellent.
In particular, if there is too much polyvinyl alcohol, the tire puncture sealant may be thickened, but if the amount of the emulsifier is within the above range, thickening is suppressed and the low-temperature injection performance can be improved.
＜バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）の製造方法＞
上記バーサチック酸ビニル共重合樹脂（ｂ１）のエマルジョンである上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）を製造する方法については、特に限定されず、例えば、バーサチック酸ビニルおよび不飽和有機酸を含むモノマーと、上記乳化剤（ｂ２）とを用いて、従来公知の乳化重合方法により製造（重合）する方法が挙げられる。
重合条件にも特に限定されないが、一般的には重合温度は２０～８０℃である。触媒としては、過硫酸カリウム等の過硫酸塩、過酸化水素および各種有機過酸化物が挙げられる。レドソックス開始系の場合は、さらに還元物質としてホルムアルデヒドナトリウムスルホキシレートなどが組み合わせて用いられる。
なお、上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）を製造するにあたっては、さらに必要に応じて、ｐＨ調整剤、増粘剤、消泡剤、分散剤、防腐剤などの添加剤を添加してもよい。 <Method for producing vinyl versatate copolymer resin emulsion (B)>
The method for producing the vinyl versatate copolymer resin emulsion (B), which is an emulsion of the vinyl versatate copolymer resin (b1), is not particularly limited. For example, a monomer containing vinyl versatate and an unsaturated organic acid And a method of producing (polymerizing) by a conventionally known emulsion polymerization method using the above-mentioned emulsifier (b2).
The polymerization conditions are not particularly limited, but generally the polymerization temperature is 20 to 80 ° C. Examples of the catalyst include persulfates such as potassium persulfate, hydrogen peroxide, and various organic peroxides. In the case of a red sox initiation system, formaldehyde sodium sulfoxylate or the like is further used in combination as a reducing substance.
In producing the above-mentioned vinyl versatate copolymer resin emulsion (B), additives such as a pH adjuster, a thickener, an antifoaming agent, a dispersant, and an antiseptic are added as necessary. Also good.
上記バーサチック酸ビニル共重合樹脂（ｂ１）のエマルジョンである上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）を製造する方法については、特に限定されず、例えば、バーサチック酸ビニルおよび不飽和有機酸を含むモノマーと、上記乳化剤（ｂ２）とを用いて、従来公知の乳化重合方法により製造（重合）する方法が挙げられる。
重合条件にも特に限定されないが、一般的には重合温度は２０～８０℃である。触媒としては、過硫酸カリウム等の過硫酸塩、過酸化水素および各種有機過酸化物が挙げられる。レドソックス開始系の場合は、さらに還元物質としてホルムアルデヒドナトリウムスルホキシレートなどが組み合わせて用いられる。
なお、上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）を製造するにあたっては、さらに必要に応じて、ｐＨ調整剤、増粘剤、消泡剤、分散剤、防腐剤などの添加剤を添加してもよい。 <Method for producing vinyl versatate copolymer resin emulsion (B)>
The method for producing the vinyl versatate copolymer resin emulsion (B), which is an emulsion of the vinyl versatate copolymer resin (b1), is not particularly limited. For example, a monomer containing vinyl versatate and an unsaturated organic acid And a method of producing (polymerizing) by a conventionally known emulsion polymerization method using the above-mentioned emulsifier (b2).
The polymerization conditions are not particularly limited, but generally the polymerization temperature is 20 to 80 ° C. Examples of the catalyst include persulfates such as potassium persulfate, hydrogen peroxide, and various organic peroxides. In the case of a red sox initiation system, formaldehyde sodium sulfoxylate or the like is further used in combination as a reducing substance.
In producing the above-mentioned vinyl versatate copolymer resin emulsion (B), additives such as a pH adjuster, a thickener, an antifoaming agent, a dispersant, and an antiseptic are added as necessary. Also good.
＜質量比（Ａ／Ｂ）＞
本発明のタイヤパンクシール剤において、上記天然ゴムラテックス（Ａ）の固形分と上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）の固形分との質量比（Ａ／Ｂ）は、９０／１０～４０／６０が好ましく、５０／５０～７０／３０がより好ましい。
上記質量比（Ａ／Ｂ）が上記範囲であれば、本発明のタイヤパンクシール剤の保管性能とシール性能とを、高いレベルで両立できる。 <Mass ratio (A / B)>
In the tire puncture sealant of the present invention, the mass ratio (A / B) of the solid content of the natural rubber latex (A) and the solid content of the vinyl versatate copolymer resin emulsion (B) is 90/10 to 40. / 60 is preferable, and 50/50 to 70/30 is more preferable.
When the mass ratio (A / B) is in the above range, the storage performance and sealing performance of the tire puncture sealant of the present invention can be achieved at a high level.
本発明のタイヤパンクシール剤において、上記天然ゴムラテックス（Ａ）の固形分と上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）の固形分との質量比（Ａ／Ｂ）は、９０／１０～４０／６０が好ましく、５０／５０～７０／３０がより好ましい。
上記質量比（Ａ／Ｂ）が上記範囲であれば、本発明のタイヤパンクシール剤の保管性能とシール性能とを、高いレベルで両立できる。 <Mass ratio (A / B)>
In the tire puncture sealant of the present invention, the mass ratio (A / B) of the solid content of the natural rubber latex (A) and the solid content of the vinyl versatate copolymer resin emulsion (B) is 90/10 to 40. / 60 is preferable, and 50/50 to 70/30 is more preferable.
When the mass ratio (A / B) is in the above range, the storage performance and sealing performance of the tire puncture sealant of the present invention can be achieved at a high level.
なお、本発明において、上記天然ゴムラテックス（Ａ）および上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）の固形分は、それぞれ、加熱残分であり、具体的には、２００℃で１時間加熱した後に得られる残存物の量である。
例えば、上記乳化剤（ｂ２）は、上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）の固形分に含まれる。 In the present invention, the solid contents of the natural rubber latex (A) and the vinyl versatate copolymer emulsion (B) are each a heating residue, specifically, heated at 200 ° C. for 1 hour. It is the amount of residue obtained later.
For example, the emulsifier (b2) is contained in the solid content of the vinyl versatate copolymer resin emulsion (B).
例えば、上記乳化剤（ｂ２）は、上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）の固形分に含まれる。 In the present invention, the solid contents of the natural rubber latex (A) and the vinyl versatate copolymer emulsion (B) are each a heating residue, specifically, heated at 200 ° C. for 1 hour. It is the amount of residue obtained later.
For example, the emulsifier (b2) is contained in the solid content of the vinyl versatate copolymer resin emulsion (B).
〔プロピレングリコール（Ｃ）〕
本発明のタイヤパンクシール剤は、さらに、凍結防止剤として、プロピレングリコール（Ｃ）を含有するのが好ましい。
このとき、上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）の固形分と上記プロピレングリコール（Ｃ）との質量比（Ｂ／Ｃ）は、０．１～１．１が好ましく、０．３～０．５がより好ましい。
上記質量比（Ｂ／Ｃ）が上記範囲であれば、本発明のタイヤパンクシール剤の保管性能とシール性能とを高いレベルで両立できる。 [Propylene glycol (C)]
The tire puncture sealant of the present invention preferably further contains propylene glycol (C) as an antifreeze agent.
At this time, the mass ratio (B / C) between the solid content of the vinyl versatate copolymer emulsion (B) and the propylene glycol (C) is preferably 0.1 to 1.1, and preferably 0.3 to 0. .5 is more preferred.
When the mass ratio (B / C) is in the above range, the storage performance and sealing performance of the tire puncture sealant of the present invention can be achieved at a high level.
本発明のタイヤパンクシール剤は、さらに、凍結防止剤として、プロピレングリコール（Ｃ）を含有するのが好ましい。
このとき、上記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）の固形分と上記プロピレングリコール（Ｃ）との質量比（Ｂ／Ｃ）は、０．１～１．１が好ましく、０．３～０．５がより好ましい。
上記質量比（Ｂ／Ｃ）が上記範囲であれば、本発明のタイヤパンクシール剤の保管性能とシール性能とを高いレベルで両立できる。 [Propylene glycol (C)]
The tire puncture sealant of the present invention preferably further contains propylene glycol (C) as an antifreeze agent.
At this time, the mass ratio (B / C) between the solid content of the vinyl versatate copolymer emulsion (B) and the propylene glycol (C) is preferably 0.1 to 1.1, and preferably 0.3 to 0. .5 is more preferred.
When the mass ratio (B / C) is in the above range, the storage performance and sealing performance of the tire puncture sealant of the present invention can be achieved at a high level.
なお、本発明のタイヤパンクシール剤は、溶媒として水を含み得るが、上記プロピレングリコール（Ｃ）と水との質量比（Ｃ／水）は、０．９～１．８が好ましい。
The tire puncture sealant of the present invention may contain water as a solvent, but the mass ratio (C / water) between the propylene glycol (C) and water is preferably 0.9 to 1.8.
〔その他の添加剤〕
本発明のタイヤパンクシール剤は、上述した各成分以外に、必要に応じて所望により、添加剤をさらに含むことができる。上記添加剤としては、例えば、上記プロピレングリコール（Ｃ）以外の凍結防止剤（例えば、エチレングリコール、ジエチレングリコール、グリセリン等）、粘着付与剤、充填剤、老化防止剤、酸化防止剤、顔料（染料）、可塑剤、揺変性付与剤、紫外線吸収剤、難燃剤、界面活性剤（レベリング剤を含む）、分散剤、脱水剤、帯電防止剤などが挙げられる。上記添加剤の量は、特に限定されない。 [Other additives]
The tire puncture sealant of the present invention may further contain an additive as required, in addition to the components described above. Examples of the additive include an antifreezing agent other than the propylene glycol (C) (for example, ethylene glycol, diethylene glycol, glycerin, etc.), a tackifier, a filler, an anti-aging agent, an antioxidant, and a pigment (dye). , Plasticizers, thixotropic agents, ultraviolet absorbers, flame retardants, surfactants (including leveling agents), dispersants, dehydrating agents, antistatic agents and the like. The amount of the additive is not particularly limited.
本発明のタイヤパンクシール剤は、上述した各成分以外に、必要に応じて所望により、添加剤をさらに含むことができる。上記添加剤としては、例えば、上記プロピレングリコール（Ｃ）以外の凍結防止剤（例えば、エチレングリコール、ジエチレングリコール、グリセリン等）、粘着付与剤、充填剤、老化防止剤、酸化防止剤、顔料（染料）、可塑剤、揺変性付与剤、紫外線吸収剤、難燃剤、界面活性剤（レベリング剤を含む）、分散剤、脱水剤、帯電防止剤などが挙げられる。上記添加剤の量は、特に限定されない。 [Other additives]
The tire puncture sealant of the present invention may further contain an additive as required, in addition to the components described above. Examples of the additive include an antifreezing agent other than the propylene glycol (C) (for example, ethylene glycol, diethylene glycol, glycerin, etc.), a tackifier, a filler, an anti-aging agent, an antioxidant, and a pigment (dye). , Plasticizers, thixotropic agents, ultraviolet absorbers, flame retardants, surfactants (including leveling agents), dispersants, dehydrating agents, antistatic agents and the like. The amount of the additive is not particularly limited.
［タイヤパンクシール剤の製造方法］
本発明のタイヤパンクシール剤を製造する方法は、特に限定されないが、例えば、上述した必須成分および任意成分を、減圧下で混合ミキサー等のかくはん機を用いて十分に混合することによってタイヤパンクシール剤を製造する方法が挙げられる。 [Method for producing tire puncture sealant]
The method for producing the tire puncture sealant of the present invention is not particularly limited. For example, the tire puncture seal is obtained by sufficiently mixing the above-described essential components and optional components using a stirring machine such as a mixing mixer under reduced pressure. The method of manufacturing an agent is mentioned.
本発明のタイヤパンクシール剤を製造する方法は、特に限定されないが、例えば、上述した必須成分および任意成分を、減圧下で混合ミキサー等のかくはん機を用いて十分に混合することによってタイヤパンクシール剤を製造する方法が挙げられる。 [Method for producing tire puncture sealant]
The method for producing the tire puncture sealant of the present invention is not particularly limited. For example, the tire puncture seal is obtained by sufficiently mixing the above-described essential components and optional components using a stirring machine such as a mixing mixer under reduced pressure. The method of manufacturing an agent is mentioned.
［タイヤパンクシール剤の使用方法］
次に、本発明のタイヤパンクシール剤の使用方法を説明する。ただし、下記方法に限定されるものではない。
まず、本発明のタイヤパンクシール剤をタイヤの空気充填部からタイヤ内に注入する。本発明のタイヤパンクシール剤をタイヤ内に注入する方法は、特に限定されず従来公知の方法を用いることができ、例えば、シリンジ、スプレー缶等を用いる方法が挙げられる。タイヤ内に注入されるタイヤパンクシール剤の量は、特に限定されず、パンク穴の大きさ等に応じて適宜選択される。
次に、所定の空気圧までタイヤに空気を充填する。
その後、車を走行させる。タイヤが回転接地する際に受ける圧縮力や剪断力によって、上記天然ゴムラテックス（Ａ）の天然ゴムや上記バーサチック酸ビニル共重合樹脂（ｂ１）の粒子等による凝集体を形成し、パンク穴をシールできる。 [How to use tire puncture sealant]
Next, a method for using the tire puncture sealant of the present invention will be described. However, it is not limited to the following method.
First, the tire puncture sealant of the present invention is injected into the tire from the air filling portion of the tire. The method for injecting the tire puncture sealant of the present invention into the tire is not particularly limited, and a conventionally known method can be used, and examples thereof include a method using a syringe, a spray can and the like. The amount of the tire puncture sealant injected into the tire is not particularly limited, and is appropriately selected according to the size of the puncture hole.
Next, the tire is filled with air to a predetermined air pressure.
Then, drive the car. By the compressive force and shearing force received when the tire is in contact with the rotating ground, an aggregate of natural rubber latex (A) natural rubber or particles of the vinyl versatate copolymer resin (b1) is formed, and the puncture hole is sealed. it can.
次に、本発明のタイヤパンクシール剤の使用方法を説明する。ただし、下記方法に限定されるものではない。
まず、本発明のタイヤパンクシール剤をタイヤの空気充填部からタイヤ内に注入する。本発明のタイヤパンクシール剤をタイヤ内に注入する方法は、特に限定されず従来公知の方法を用いることができ、例えば、シリンジ、スプレー缶等を用いる方法が挙げられる。タイヤ内に注入されるタイヤパンクシール剤の量は、特に限定されず、パンク穴の大きさ等に応じて適宜選択される。
次に、所定の空気圧までタイヤに空気を充填する。
その後、車を走行させる。タイヤが回転接地する際に受ける圧縮力や剪断力によって、上記天然ゴムラテックス（Ａ）の天然ゴムや上記バーサチック酸ビニル共重合樹脂（ｂ１）の粒子等による凝集体を形成し、パンク穴をシールできる。 [How to use tire puncture sealant]
Next, a method for using the tire puncture sealant of the present invention will be described. However, it is not limited to the following method.
First, the tire puncture sealant of the present invention is injected into the tire from the air filling portion of the tire. The method for injecting the tire puncture sealant of the present invention into the tire is not particularly limited, and a conventionally known method can be used, and examples thereof include a method using a syringe, a spray can and the like. The amount of the tire puncture sealant injected into the tire is not particularly limited, and is appropriately selected according to the size of the puncture hole.
Next, the tire is filled with air to a predetermined air pressure.
Then, drive the car. By the compressive force and shearing force received when the tire is in contact with the rotating ground, an aggregate of natural rubber latex (A) natural rubber or particles of the vinyl versatate copolymer resin (b1) is formed, and the puncture hole is sealed. it can.
以下、実施例を示して本発明を具体的に説明する。ただし、本発明はこれらに限定されない。
Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these.
＜バーサチック酸ビニル共重合樹脂エマルジョンの製造＞
投入成分量を適宜変更して、「モノマー質量比」および「乳化剤量」を異ならせた複数種類の不飽和有機酸（アクリル酸またはマレイン酸）－エチレン－酢酸ビニル－バーサチック酸ビニル共重合樹脂エマルジョン（以下、単に、「バーサチック酸ビニル共重合樹脂エマルジョン」という）を得た。
具体的には、耐圧容器に、水、アクリル酸またはマレイン酸、酢酸ビニル、バーサチック酸ビニル、ポリビニルアルコール（ポバール２０５、クラレ社製、ケン化度８８モル％、平均重合度：５００）、ノニオン界面活性剤（ポリオキシエチレンアルキルエーテル、エマルゲン１１０８、花王社製)、および、硫酸第一鉄七水和物を溶解した溶液を添加した。
次に、耐圧容器内を窒素ガスで置換し、容器内を４５℃まで昇温した後、エチレンで６．０ＭＰａまで加圧し、５％過硫酸ナトリウム水溶液を添加し、７％エリソルビン酸ナトリウム水溶液を耐圧容器に添加して重合を開始させた。
続いて、耐圧容器内の液温が上昇したことを確認した後、容器内の液温を５０℃に維持しながら、重合開始後４時間経過した時点で、酸化剤を１０％過硫酸ナトリウムおよび２％ｔｅｒｔ－ブチルハイドロパーオキサイド水溶液に切り替え、耐圧容器に添加し、残留酢酸ビニル単量体が１％未満になった時点で耐圧容器を冷却し、未反応のエチレンガスを除去した後、生成物を取り出した。このようにして、バーサチック酸ビニル共重合樹脂エマルジョンを得た。固形分は５３質量％、ガラス転移温度は－３０℃であった。 <Manufacture of a vinyl versatate copolymer resin emulsion>
Multiple types of unsaturated organic acids (acrylic acid or maleic acid) -ethylene-vinyl acetate-vinyl versatate copolymer resin emulsions with different amounts of charged components and different “mass ratio” and “emulsifier amount” (Hereinafter simply referred to as “vinyl versatate copolymer emulsion”).
Specifically, water, acrylic acid or maleic acid, vinyl acetate, vinyl versatate, polyvinyl alcohol (Poval 205, manufactured by Kuraray Co., Ltd., saponification degree 88 mol%, average polymerization degree: 500), nonionic interface An activator (polyoxyethylene alkyl ether, Emulgen 1108, manufactured by Kao Corporation) and a solution in which ferrous sulfate heptahydrate was dissolved were added.
Next, the inside of the pressure vessel is replaced with nitrogen gas, and the temperature inside the vessel is raised to 45 ° C., then pressurized to 6.0 MPa with ethylene, 5% sodium persulfate aqueous solution is added, and 7% sodium erythorbate aqueous solution is added. Polymerization was started by adding to a pressure vessel.
Subsequently, after confirming that the liquid temperature in the pressure resistant vessel had risen, while maintaining the liquid temperature in the vessel at 50 ° C., when 4 hours had elapsed after the start of polymerization, the oxidizing agent was added with 10% sodium persulfate and Switch to 2% tert-butyl hydroperoxide aqueous solution, add to the pressure vessel, cool the pressure vessel when the residual vinyl acetate monomer is less than 1%, remove unreacted ethylene gas, and generate The thing was taken out. In this way, a vinyl versatate copolymer resin emulsion was obtained. The solid content was 53% by mass and the glass transition temperature was −30 ° C.
投入成分量を適宜変更して、「モノマー質量比」および「乳化剤量」を異ならせた複数種類の不飽和有機酸（アクリル酸またはマレイン酸）－エチレン－酢酸ビニル－バーサチック酸ビニル共重合樹脂エマルジョン（以下、単に、「バーサチック酸ビニル共重合樹脂エマルジョン」という）を得た。
具体的には、耐圧容器に、水、アクリル酸またはマレイン酸、酢酸ビニル、バーサチック酸ビニル、ポリビニルアルコール（ポバール２０５、クラレ社製、ケン化度８８モル％、平均重合度：５００）、ノニオン界面活性剤（ポリオキシエチレンアルキルエーテル、エマルゲン１１０８、花王社製)、および、硫酸第一鉄七水和物を溶解した溶液を添加した。
次に、耐圧容器内を窒素ガスで置換し、容器内を４５℃まで昇温した後、エチレンで６．０ＭＰａまで加圧し、５％過硫酸ナトリウム水溶液を添加し、７％エリソルビン酸ナトリウム水溶液を耐圧容器に添加して重合を開始させた。
続いて、耐圧容器内の液温が上昇したことを確認した後、容器内の液温を５０℃に維持しながら、重合開始後４時間経過した時点で、酸化剤を１０％過硫酸ナトリウムおよび２％ｔｅｒｔ－ブチルハイドロパーオキサイド水溶液に切り替え、耐圧容器に添加し、残留酢酸ビニル単量体が１％未満になった時点で耐圧容器を冷却し、未反応のエチレンガスを除去した後、生成物を取り出した。このようにして、バーサチック酸ビニル共重合樹脂エマルジョンを得た。固形分は５３質量％、ガラス転移温度は－３０℃であった。 <Manufacture of a vinyl versatate copolymer resin emulsion>
Multiple types of unsaturated organic acids (acrylic acid or maleic acid) -ethylene-vinyl acetate-vinyl versatate copolymer resin emulsions with different amounts of charged components and different “mass ratio” and “emulsifier amount” (Hereinafter simply referred to as “vinyl versatate copolymer emulsion”).
Specifically, water, acrylic acid or maleic acid, vinyl acetate, vinyl versatate, polyvinyl alcohol (Poval 205, manufactured by Kuraray Co., Ltd., saponification degree 88 mol%, average polymerization degree: 500), nonionic interface An activator (polyoxyethylene alkyl ether, Emulgen 1108, manufactured by Kao Corporation) and a solution in which ferrous sulfate heptahydrate was dissolved were added.
Next, the inside of the pressure vessel is replaced with nitrogen gas, and the temperature inside the vessel is raised to 45 ° C., then pressurized to 6.0 MPa with ethylene, 5% sodium persulfate aqueous solution is added, and 7% sodium erythorbate aqueous solution is added. Polymerization was started by adding to a pressure vessel.
Subsequently, after confirming that the liquid temperature in the pressure resistant vessel had risen, while maintaining the liquid temperature in the vessel at 50 ° C., when 4 hours had elapsed after the start of polymerization, the oxidizing agent was added with 10% sodium persulfate and Switch to 2% tert-butyl hydroperoxide aqueous solution, add to the pressure vessel, cool the pressure vessel when the residual vinyl acetate monomer is less than 1%, remove unreacted ethylene gas, and generate The thing was taken out. In this way, a vinyl versatate copolymer resin emulsion was obtained. The solid content was 53% by mass and the glass transition temperature was −30 ° C.
＜タイヤパンクシール剤の製造＞
下記第１表に示す成分を、同表に示す量（質量部）で用いて、これらを混合することによってタイヤパンクシール剤を製造した。
このとき、（Ｂ）成分として、上記のようにして製造したバーサチック酸ビニル共重合樹脂エマルジョンを用いた。用いたバーサチック酸ビニル共重合樹脂エマルジョンの「モノマー質量比」および「乳化剤量」を下記第１表に示す。使用しなかったモノマーについては「－」を記載した。
なお、下記第１表中、（Ａ）および（Ｂ）成分における下段の数値（括弧内の数値）は、それぞれ、固形分換算した配合量を、（Ａ）および（Ｂ）成分の合計固形分を１００質量部とした場合の相対的な値で表したものである（単位は質量部）。
また、タイヤパンクシール剤を製造する際に必要に応じて水を添加した。下記第１表に示す水の量はタイヤパンクシール剤全量中に含まれるトータルの水の量である。 <Manufacture of tire puncture sealants>
A tire puncture sealant was produced by mixing the components shown in Table 1 below in the amounts (parts by mass) shown in the same table.
At this time, the vinyl versatate copolymer resin emulsion produced as described above was used as the component (B). The “monomer mass ratio” and “emulsifier amount” of the vinyl versatate copolymer resin emulsion used are shown in Table 1 below. Monomers that were not used were marked with “-”.
In Table 1 below, the lower numerical values (the numerical values in parentheses) in the components (A) and (B) are the total solid content of the components (A) and (B), respectively, in terms of the solid content. Is expressed as a relative value when 100 parts by mass is used (unit is part by mass).
Moreover, water was added as needed when producing the tire puncture sealant. The amount of water shown in Table 1 below is the total amount of water contained in the total amount of the tire puncture sealant.
下記第１表に示す成分を、同表に示す量（質量部）で用いて、これらを混合することによってタイヤパンクシール剤を製造した。
このとき、（Ｂ）成分として、上記のようにして製造したバーサチック酸ビニル共重合樹脂エマルジョンを用いた。用いたバーサチック酸ビニル共重合樹脂エマルジョンの「モノマー質量比」および「乳化剤量」を下記第１表に示す。使用しなかったモノマーについては「－」を記載した。
なお、下記第１表中、（Ａ）および（Ｂ）成分における下段の数値（括弧内の数値）は、それぞれ、固形分換算した配合量を、（Ａ）および（Ｂ）成分の合計固形分を１００質量部とした場合の相対的な値で表したものである（単位は質量部）。
また、タイヤパンクシール剤を製造する際に必要に応じて水を添加した。下記第１表に示す水の量はタイヤパンクシール剤全量中に含まれるトータルの水の量である。 <Manufacture of tire puncture sealants>
A tire puncture sealant was produced by mixing the components shown in Table 1 below in the amounts (parts by mass) shown in the same table.
At this time, the vinyl versatate copolymer resin emulsion produced as described above was used as the component (B). The “monomer mass ratio” and “emulsifier amount” of the vinyl versatate copolymer resin emulsion used are shown in Table 1 below. Monomers that were not used were marked with “-”.
In Table 1 below, the lower numerical values (the numerical values in parentheses) in the components (A) and (B) are the total solid content of the components (A) and (B), respectively, in terms of the solid content. Is expressed as a relative value when 100 parts by mass is used (unit is part by mass).
Moreover, water was added as needed when producing the tire puncture sealant. The amount of water shown in Table 1 below is the total amount of water contained in the total amount of the tire puncture sealant.
＜評価＞
得られたタイヤパンクシール剤について、以下の評価を行った。結果を下記第１表に示す。 <Evaluation>
The obtained tire puncture sealant was evaluated as follows. The results are shown in Table 1 below.
得られたタイヤパンクシール剤について、以下の評価を行った。結果を下記第１表に示す。 <Evaluation>
The obtained tire puncture sealant was evaluated as follows. The results are shown in Table 1 below.
（シール性能）
得られたパンクシール剤を用いて、シール性能を評価した。
具体的には、まず、タイヤのショルダー部に直径４ｍｍの大きさのパンク孔を再現した。次いで、パンク孔を再現したタイヤをドラム試験機に装着し、タイヤのバルブ口からタイヤパンクシール剤を注入し、タイヤ内圧が２００ｋＰａになるように空気を充填して、雰囲気温度を２５℃（常温）として、ドラム試験を行なった。ドラム試験は、荷重３５０ｋｇ、走行速度３０ｋｍ／ｈ、走行時間１分とし、これを１サイクルとした。
シール性能の評価基準は、５サイクル以内でシールできた（空気漏れがなくなった）場合を「◎」、６～１０サイクルでシールできた場合を「○」、１１サイクル以上でシールできた場合を「△」、シールできなかった場合を「×」とした。「◎」または「○」であれば、シール性能に優れるものとして評価できる。 (Seal performance)
Sealing performance was evaluated using the obtained puncture sealant.
Specifically, first, a puncture hole having a diameter of 4 mm was reproduced in the shoulder portion of the tire. Next, a tire that reproduces the puncture hole is mounted on a drum testing machine, a tire puncture sealant is injected from the valve port of the tire, and air is filled so that the tire internal pressure becomes 200 kPa. ) As a drum test. In the drum test, a load of 350 kg, a traveling speed of 30 km / h, and a traveling time of 1 minute were set as one cycle.
The evaluation criteria for sealing performance are “◎” when the seal was completed within 5 cycles (no air leaks), “○” when the seal was sealed within 6 to 10 cycles, and when the seal was completed after 11 cycles. “Δ”, and “x” when the seal could not be made. If “◎” or “○”, it can be evaluated as having excellent sealing performance.
得られたパンクシール剤を用いて、シール性能を評価した。
具体的には、まず、タイヤのショルダー部に直径４ｍｍの大きさのパンク孔を再現した。次いで、パンク孔を再現したタイヤをドラム試験機に装着し、タイヤのバルブ口からタイヤパンクシール剤を注入し、タイヤ内圧が２００ｋＰａになるように空気を充填して、雰囲気温度を２５℃（常温）として、ドラム試験を行なった。ドラム試験は、荷重３５０ｋｇ、走行速度３０ｋｍ／ｈ、走行時間１分とし、これを１サイクルとした。
シール性能の評価基準は、５サイクル以内でシールできた（空気漏れがなくなった）場合を「◎」、６～１０サイクルでシールできた場合を「○」、１１サイクル以上でシールできた場合を「△」、シールできなかった場合を「×」とした。「◎」または「○」であれば、シール性能に優れるものとして評価できる。 (Seal performance)
Sealing performance was evaluated using the obtained puncture sealant.
Specifically, first, a puncture hole having a diameter of 4 mm was reproduced in the shoulder portion of the tire. Next, a tire that reproduces the puncture hole is mounted on a drum testing machine, a tire puncture sealant is injected from the valve port of the tire, and air is filled so that the tire internal pressure becomes 200 kPa. ) As a drum test. In the drum test, a load of 350 kg, a traveling speed of 30 km / h, and a traveling time of 1 minute were set as one cycle.
The evaluation criteria for sealing performance are “◎” when the seal was completed within 5 cycles (no air leaks), “○” when the seal was sealed within 6 to 10 cycles, and when the seal was completed after 11 cycles. “Δ”, and “x” when the seal could not be made. If “◎” or “○”, it can be evaluated as having excellent sealing performance.
（保管性能）
８０℃雰囲気下において、タイヤパンクシール剤に２０Ｈｚ、振幅±３ｍｍの振動を１６８時間与える試験を行なった。
保管性能の評価基準は、クリームの発生なしで安定している場合を「◎」、クリームが発生したがタイヤパンクシール剤を撹拌すればクリームが消失し均一となった場合を「○」、凝集物が発生した場合を「×」とした。「◎」または「○」であれば、保管性能に優れるものとして評価できる。 (Storage performance)
In an 80 ° C. atmosphere, a test was performed in which a tire puncture sealant was subjected to vibrations of 20 Hz and amplitude of ± 3 mm for 168 hours.
The evaluation criteria for storage performance are: “◎” when the cream is stable without the occurrence of cream, “○” when the cream is generated, but the cream disappears and becomes uniform if the tire puncture sealant is stirred, agglomeration The case where an object was generated was designated as “x”. If “◎” or “○”, it can be evaluated as having excellent storage performance.
８０℃雰囲気下において、タイヤパンクシール剤に２０Ｈｚ、振幅±３ｍｍの振動を１６８時間与える試験を行なった。
保管性能の評価基準は、クリームの発生なしで安定している場合を「◎」、クリームが発生したがタイヤパンクシール剤を撹拌すればクリームが消失し均一となった場合を「○」、凝集物が発生した場合を「×」とした。「◎」または「○」であれば、保管性能に優れるものとして評価できる。 (Storage performance)
In an 80 ° C. atmosphere, a test was performed in which a tire puncture sealant was subjected to vibrations of 20 Hz and amplitude of ± 3 mm for 168 hours.
The evaluation criteria for storage performance are: “◎” when the cream is stable without the occurrence of cream, “○” when the cream is generated, but the cream disappears and becomes uniform if the tire puncture sealant is stirred, agglomeration The case where an object was generated was designated as “x”. If “◎” or “○”, it can be evaluated as having excellent storage performance.
（低温注入性能）
得られたタイヤパンクシール剤の粘度を、－４０℃の条件下で、ＢＬ型粘度計（ローターＮｏ．４）を用いて回転数６０ｒｐｍで測定した。
－４０℃におけるタイヤパンクシール剤の粘度が、２０００ｍＰａ・ｓ以上３０００ｍＰａ・ｓ未満の場合を「◎」、３０００ｍＰａ・ｓ以上４０００ｍＰａ・ｓ未満の場合を「○」、４０００ｍＰａ・ｓ以上の場合を「×」とした。「◎」または「○」であれば、低温特性である低温注入性能に優れるものとして評価できる。 (Low temperature injection performance)
The viscosity of the obtained tire puncture sealant was measured at a rotational speed of 60 rpm using a BL type viscometer (rotor No. 4) under the condition of −40 ° C.
The case where the viscosity of the tire puncture sealant at −40 ° C. is 2000 mPa · s or more and less than 3000 mPa · s is “A”, the case where it is 3000 mPa · s or more and less than 4000 mPa · s is “◯”, × ”. If “◎” or “◯”, it can be evaluated as having excellent low-temperature injection performance, which is a low-temperature characteristic.
得られたタイヤパンクシール剤の粘度を、－４０℃の条件下で、ＢＬ型粘度計（ローターＮｏ．４）を用いて回転数６０ｒｐｍで測定した。
－４０℃におけるタイヤパンクシール剤の粘度が、２０００ｍＰａ・ｓ以上３０００ｍＰａ・ｓ未満の場合を「◎」、３０００ｍＰａ・ｓ以上４０００ｍＰａ・ｓ未満の場合を「○」、４０００ｍＰａ・ｓ以上の場合を「×」とした。「◎」または「○」であれば、低温特性である低温注入性能に優れるものとして評価できる。 (Low temperature injection performance)
The viscosity of the obtained tire puncture sealant was measured at a rotational speed of 60 rpm using a BL type viscometer (rotor No. 4) under the condition of −40 ° C.
The case where the viscosity of the tire puncture sealant at −40 ° C. is 2000 mPa · s or more and less than 3000 mPa · s is “A”, the case where it is 3000 mPa · s or more and less than 4000 mPa · s is “◯”, × ”. If “◎” or “◯”, it can be evaluated as having excellent low-temperature injection performance, which is a low-temperature characteristic.
上記第１表に示す各成分の詳細は以下のとおりである。
・天然ゴムラテックス：Ｈｙｔｅｘ ＨＡ（野村貿易社製、固形分約６０質量％）
・バーサチック酸ビニル共重合樹脂エマルジョン：上述したもの
・プロピレングリコール：試薬１級、和光純薬社製 The details of each component shown in Table 1 are as follows.
・ Natural rubber latex: Hytex HA (Nomura Trading Co., Ltd., solid content: about 60% by mass)
・ Veracic acid vinyl copolymer resin emulsion: as described above ・ Propylene glycol: Reagent grade 1, manufactured by Wako Pure Chemical Industries, Ltd.
・天然ゴムラテックス：Ｈｙｔｅｘ ＨＡ（野村貿易社製、固形分約６０質量％）
・バーサチック酸ビニル共重合樹脂エマルジョン：上述したもの
・プロピレングリコール：試薬１級、和光純薬社製 The details of each component shown in Table 1 are as follows.
・ Natural rubber latex: Hytex HA (Nomura Trading Co., Ltd., solid content: about 60% by mass)
・ Veracic acid vinyl copolymer resin emulsion: as described above ・ Propylene glycol: Reagent grade 1, manufactured by Wako Pure Chemical Industries, Ltd.
上記第１表に示す比較例１～４を見ると、比較例１を基準として、乳化剤量を低減することで、低温注入性能が改善される一方、保管性能が劣ることが分かった。
これに対して、実施例１～６および実施例９～１１では、乳化剤量を比較例４と同等以下に低減しても、不飽和有機酸（アクリル酸またはマレイン酸）を共重合させた（Ｂ）成分を用いることで、良好な保管性能を維持したまま、低温注入性能を向上できることが分かった。
また、実施例７および８の結果からは、乳化剤量を低減させなくても、不飽和有機酸を共重合させた（Ｂ）成分を用いることで、低温注入性能が向上できることが分かった。 By looking at Comparative Examples 1 to 4 shown in Table 1 above, it was found that reducing the amount of emulsifier on the basis of Comparative Example 1 improved the low-temperature injection performance while inferior storage performance.
On the other hand, in Examples 1 to 6 and Examples 9 to 11, an unsaturated organic acid (acrylic acid or maleic acid) was copolymerized even when the amount of the emulsifier was reduced to the same level or lower as in Comparative Example 4 ( It was found that by using the component B), the low temperature injection performance can be improved while maintaining good storage performance.
Further, from the results of Examples 7 and 8, it was found that the low-temperature injection performance can be improved by using the component (B) obtained by copolymerizing an unsaturated organic acid without reducing the amount of the emulsifier.
これに対して、実施例１～６および実施例９～１１では、乳化剤量を比較例４と同等以下に低減しても、不飽和有機酸（アクリル酸またはマレイン酸）を共重合させた（Ｂ）成分を用いることで、良好な保管性能を維持したまま、低温注入性能を向上できることが分かった。
また、実施例７および８の結果からは、乳化剤量を低減させなくても、不飽和有機酸を共重合させた（Ｂ）成分を用いることで、低温注入性能が向上できることが分かった。 By looking at Comparative Examples 1 to 4 shown in Table 1 above, it was found that reducing the amount of emulsifier on the basis of Comparative Example 1 improved the low-temperature injection performance while inferior storage performance.
On the other hand, in Examples 1 to 6 and Examples 9 to 11, an unsaturated organic acid (acrylic acid or maleic acid) was copolymerized even when the amount of the emulsifier was reduced to the same level or lower as in Comparative Example 4 ( It was found that by using the component B), the low temperature injection performance can be improved while maintaining good storage performance.
Further, from the results of Examples 7 and 8, it was found that the low-temperature injection performance can be improved by using the component (B) obtained by copolymerizing an unsaturated organic acid without reducing the amount of the emulsifier.
Claims (5)
- 天然ゴムラテックス（Ａ）と、バーサチック酸ビニルおよび不飽和有機酸をモノマー単位として含むバーサチック酸ビニル共重合樹脂（ｂ１）のエマルジョンであるバーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）と、を含有するタイヤパンクシール剤。 Tire containing natural rubber latex (A) and vinyl versatate copolymer emulsion (B) which is an emulsion of vinyl versatate copolymer resin (b1) containing vinyl versatate and unsaturated organic acid as monomer units Punk sealant.
- 前記バーサチック酸ビニル共重合樹脂（ｂ１）を構成する全モノマー単位に対する前記不飽和有機酸の割合が、０．０１～２．００質量％である、請求項１に記載のタイヤパンクシール剤。 2. The tire puncture sealant according to claim 1, wherein a ratio of the unsaturated organic acid to all monomer units constituting the vinyl versatate copolymer resin (b1) is 0.01 to 2.00% by mass.
- 前記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）が、ポリビニルアルコールを含む乳化剤（ｂ２）を含有し、
前記乳化剤（ｂ２）の含有量が、前記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）の固形分に対して、０．８～３．０質量％である、請求項１または２に記載のタイヤパンクシール剤。 The versatic acid vinyl copolymer resin emulsion (B) contains an emulsifier (b2) containing polyvinyl alcohol,
The tire puncture according to claim 1 or 2, wherein a content of the emulsifier (b2) is 0.8 to 3.0 mass% with respect to a solid content of the vinyl versatate copolymer resin emulsion (B). Sealing agent. - 前記バーサチック酸ビニル共重合樹脂（ｂ１）が、不飽和有機酸－エチレン－酢酸ビニル－バーサチック酸ビニル共重合樹脂である、請求項１～３のいずれかに記載のタイヤパンクシール剤。 The tire puncture sealant according to any one of claims 1 to 3, wherein the vinyl versatate copolymer resin (b1) is an unsaturated organic acid-ethylene-vinyl acetate-vinyl versatate copolymer resin.
- 前記天然ゴムラテックス（Ａ）の固形分と前記バーサチック酸ビニル共重合樹脂エマルジョン（Ｂ）の固形分との質量比（Ａ／Ｂ）が、９０／１０～４０／６０である、請求項１～４のいずれかに記載のタイヤパンクシール剤。 The mass ratio (A / B) between the solid content of the natural rubber latex (A) and the solid content of the vinyl versatate copolymer resin emulsion (B) is 90/10 to 40/60. 5. The tire puncture sealant according to any one of 4 above.
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| CN201480043772.1A CN105452415B (en) | 2013-08-09 | 2014-08-07 | Tyre puncture sealant |
| DE112014003690.0T DE112014003690B4 (en) | 2013-08-09 | 2014-08-07 | Tire puncture sealant |
| KR1020167003261A KR101609745B1 (en) | 2013-08-09 | 2014-08-07 | Flat tire sealant |
| US14/910,865 US9656431B2 (en) | 2013-08-09 | 2014-08-07 | Tire puncture sealant |
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| JP2013166301A JP5664723B1 (en) | 2013-08-09 | 2013-08-09 | Tire puncture sealant |
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| JP (1) | JP5664723B1 (en) |
| KR (1) | KR101609745B1 (en) |
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| JP6299844B1 (en) * | 2016-11-10 | 2018-03-28 | 横浜ゴム株式会社 | Tire puncture sealant and tire puncture repair kit |
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| JP2011026533A (en) * | 2009-06-22 | 2011-02-10 | Yokohama Rubber Co Ltd:The | Tire puncture sealing material |
| JP2013040297A (en) * | 2011-08-18 | 2013-02-28 | Yokohama Rubber Co Ltd:The | Tire puncture sealing agent |
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| DE19652546B4 (en) | 1996-12-17 | 2012-11-22 | Sumitomo Rubber Industries Ltd. | Means for sealing tires during breakdowns, devices for sealing and inflating tires and tires with integrated sealing means |
| EP1757658A4 (en) * | 2004-04-28 | 2010-09-01 | Mitsui Chemicals Inc | Rubber composition and use thereof |
| EP1825991B1 (en) * | 2006-02-27 | 2014-04-02 | The Yokohama Rubber Co., Ltd. | Tire puncture sealant |
| JP4245654B2 (en) * | 2007-07-17 | 2009-03-25 | 横浜ゴム株式会社 | Emulsion coagulant |
| US8623462B2 (en) * | 2008-06-27 | 2014-01-07 | Akzo Nobel N.V. | Redispersible polymer powder composition |
| JP4609598B1 (en) * | 2009-06-22 | 2011-01-12 | 横浜ゴム株式会社 | Tire puncture sealant |
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| JP4752982B1 (en) * | 2010-02-04 | 2011-08-17 | 横浜ゴム株式会社 | Tire puncture sealant |
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| JP5316607B2 (en) * | 2010-08-11 | 2013-10-16 | 横浜ゴム株式会社 | Tire puncture sealant |
| ITTO20101031A1 (en) * | 2010-12-21 | 2012-06-22 | Tek Global Srl | SEALANT COMPOSITION FOR REPAIRING TIRES |
| US9296887B2 (en) * | 2011-03-15 | 2016-03-29 | The Nippon Synthetic Chemical Industry Co., Ltd. | Resin composition and molded product thereof |
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| JP5664722B1 (en) * | 2013-08-09 | 2015-02-04 | 横浜ゴム株式会社 | Tire puncture sealant |
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| JP2011026533A (en) * | 2009-06-22 | 2011-02-10 | Yokohama Rubber Co Ltd:The | Tire puncture sealing material |
| JP2013040297A (en) * | 2011-08-18 | 2013-02-28 | Yokohama Rubber Co Ltd:The | Tire puncture sealing agent |
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| CN105452415B (en) | 2018-04-17 |
| KR101609745B1 (en) | 2016-04-06 |
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| DE112014003690B4 (en) | 2020-01-30 |
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